Water-soluble sulfur dyestuffs

ABSTRACT

Water-soluble dyestuffs having an affinity for fibers and being capable to dyeing in the absence of reducing agents obtained by reacting water-insoluble sulfur dyestuffs, reduction products thereof or their thiosulfuric acid derivatives with alkylenimines and substituted derivatives thereof.

United States Patent 91 Engelhardt et al.

[ WATER-SOLUBLE SULFUR DYESTUFFS [75] Inventors: Friedrich Engelhardt; Christian Heid, both of Frankfurt am Main- Fechenheim; Willi Gunzert, Frankfurt am Main; Erwin Kruache; Artur Meyer, both of Frankfurt am Main- Fechenhaim, all of Germany [73] Assignee: Cassella Farbwerke Mainkur Aktleugesellschait, Frankfurt am Main- Fechenheim, Germany [22] Filed: Dec. 15, 1969 [21] Appl. No.: 885,322

[30] Foreign Application Priority Data Dec. 17,1968 Germany ..P l8 15 I332 52 1 ES: Ci. IT. I)": ..IlfiiifiliiiitT/iifi' Feb. 13, 1973 Primary Examiner-Lewis Gotts Assistant Examiner-D. R. Phillips Attorney-Connolly and Hutz [5 7 ABSTRACT Water-soluble dyestuffs having an affinity for fibers and being capable to dyeing in the absence of reducing agents obtained by reacting water-insoluble sulfur dyestuffs, reduction products thereof or their thiosulfuric acid derivatives with alkylenimines and substituted derivatives thereof.

5 Claims, No Drawings WATER-SOLUBLE SULFUR DYESTUFFS in practice, the water-insoluble sulfur dyestuffs are dissolved with sulfur alkalies, in particular with sodium sulfide, applied to cellulose containing textiles in the form of their leuco compounds from the thusly obtained dyeing liquors and the insoluble sulfur dyestuffs are then fixed onto the fiber by a subsequent oxidation process.

Dyeing with the water-soluble thiosulfuric acids of the sulfur dyestuffs is carried out similarly. This process, too, requires sulfur alkalies in order to split off the thiosulfuric acid residues with the formation of the leuco compounds having an affinity for fibers and, thus, to enable the dyestuff to go onto the fibers.

The above dyeing methods necessarily involve the formation of rather large amounts of highly sulfur-containing waste water which are difficult to purify. Consequently, for some time, efforts have been made to develop methods which would allow fixing sulfur dyestuffs onto cellulosic textiles without the addition of reducing agents.

British Pat. No. 787,878 describes a method according to which fixation may be achieved by padding cotton and regenerated cellulose with the solutions of the water-soluble thiosulfuric acid derivatives of sulfur dyestuffs being free from reducing agents and subsequently heating the padded material to an elevated temperature. This method is, however, inferior to the above methods comprising the addition of sulfur alkalies, with regard to the fixation of the dyestuffs and the fastness properties of the dyeings obtained therewith. Furthermore, US. Pat. No. 3,294,476 describes a method that consists of padding the textiles with dye liquors containing, in addition to the water-soluble thiosulfuric acids of the sulfur dyestuffs or their salts, bior poly-functional substances that yield together with the sulfur dyestuffs stable reaction products and may, moreover, contain acid or alkaline catalysts, submitting, if required, the thusly treated textiles, after drying, to a moist or dry-heat treatment and finishing them as usual. One drawback consists, however, in that the thiosulfuric acids of the sulfur dyestuffs have no affinity for cellulose fibers when applied without the addition of reducing agents and, consequently, cannot be dyed according to the exhaust process.

It has now been found that water-soluble sulfur dyestuffs having an affinity for fibers and being capable of dyeing in the absence of reducing agents are obtained by reacting, preferably in the presence of catalysts, water-insoluble sulfur dyestuffs, reduction products thereof or a thiosulfuric acid derivative thereof with alkylenimines that may be substituted. Ethylenimine is particularly preferred.

Apart from ethylenimine, particularly suited for the process of the present invention are, for instance, 1,2- propylenimine, N-acetylethylenimine, )8- ethyleniminopropionamide, N-methylethylenimine, 2,2-dimethylethylenimine, 2,3-dimethylethylenimine, methyl-B-ethyleniminepropionate and 2- ethylethylenimine. Catalysts having a favorableeffect on the reaction are, for instance, ethylenechloride and epichlorhydrin.

The reaction with the alkylenimines is carried out at temperatures ranging from about to 120 C., preferentially about 40 to 120 C. Preferably, it is carried out in an aqueous medium or in an organic solvent, preferably a lower alkanol or dimethylformamide, which may be diluted with water, whereby the initial dyestuffs are either present in the form of a suspension or may be dissolved partly or in total.

lf water-insoluble sulfur dyestuffs are employed as initial dyestuffs and the reaction is terminated, i.e., a sample of the reaction products dissolves without leaving a residue in water which may be weakly acidified, unreacted alkylenimine, if any, may be polymerized by the addition of a catalyst, such as ethylenechloride or epichlorhydrin and by the introduction of CO or $0,.

in order that sulfur dyes are obtained that dissolve already in neutral water the reaction mixture is, when the reaction is terminated, adjusted to an acid pH, preferably to pH of about 4 to 5. If the mixture does not show an acid reaction at the end of the reaction period there are obtained sulfur dyes that readily dissolve in acidified, preferentially in acetified water. Towards the end of the reaction period, a pH of about 4 to 5 can be attained advantageously by passing CO, or S0 into the reaction mixture. Consequently, during the reaction the pH value of the reaction mixture falls from the alkaline into the neutral range and finally to a pH of about 4 to 5. The CO or SO, passed in has a catalytic effect on the exothermic reaction whereby presumably part of the alkylenimine simultaneously reacts with polymerization.

The sulfur dyestuffs obtained according to the process of the present invention are obtained in the form of more or less viscous pastes being easily soluble in water that may be weakly acidified. They have an affinity for cellulose fibers and, consequently, may be employed without the addition of reducing agents for the dyeing of cellulosic textiles according to the exhaust process. Moreover, they may be padded, for in stance, onto cellulose materials, whereby the fixation of the dyestuffs may be achieved, after an intermediate drying, if required, by moist or dry-heat treatment.

Thus obtained in an easy way and without the formation of sulfur-containing waste water, are deep dyeings that distinguish themselves by good fastness properties, in particular by an excellent fastness to wet processing.

The following Examples are given for the purpose of illustrating the present invention. All temperatures are given in degrees Centigrade.

EXAMPLE I a. 100 g. Hydrosol Fast Yellow G (Color lnd. Solubilized Sulfur Yellow 5; thiosulfuric acid from lmmedial Fast Yellow GWL, the constitution of which is described in Coll. Czech. Chem. Comm. 27 (1962) 1,533-48) are suspended in c.c. water. Subsequently, 48 c.c. ethylenimine are added dropwise with stirring at room temperature and the reaction vessel is put into a bath which was heated to 80. When the temperature of the reaction mixture has reached 55, 0,7 c.c. epichlorhydrin are added and a weak CO gas stream is introduced. The temperature then rises automatically within 15 minutes to 99. Subsequently, the introduction of CO, gas is stopped and the reaction mixture is stirred for another hour at 100. Thus, there is obtained, after cooling down, a brown, viscous dye paste that is easily soluble in water.

b. l g. of this dye paste is dissolved in approximately 50 c.c. water of 50-60 and filled up with cold water to give 200 c.c. The thusly prepared dyebath is adjusted with acetic acid to a pH value of 7. At 25-30, a cotton hank is introduced and moved in the bath. The liquor ratio is 1:20. Then the temperature of the dyebath is elevated during approximately 30 minutes to 90-95 and the cotton hank which is moved from time to time, is dyed during 1 hour at this temperature, until the dyestuff has gone onto the material. Subsequently, the dyed hank is thoroughly rinsed and dried. Thus obtained is a deep yellow dyeing having a good fastness to wet processing.

An even better exhaustion of the dyestuff is achieved by the addition of 3 g./l. urea to the dyebath.

EXAMPLE 2 100 g. Hydrosol Fast Yellow G (see Example 1a) are pasted on with 40 c.c. water and than 60 c.c. ethylenimine are added. After the addition of 0.3 c.c. ethylenechloride, a CO, gas stream is introduced into the reaction mixture at 40. The reaction that takes place is exothermic, whereby the temperature rises in the course of 18 minutes to 106. The introduction of CO, gas is then cut off and stirring is continued for another 4 hours at a bath temperature of 100.

The viscous brown dye paste being formed is easily soluble in water. lts behavior with regard to the dyeing properties is similar to that of the dye paste obtained according to Example 1.

EXAMPLE 3 100 g. Hydrosol Fast Yellow G (see Examplela) are suspended in 80 c.c. water. After the addition of 48 c.c. ethylenimine and 0.2 c.c. aqueous hydrochloric acid 10 N, the reaction mixture is slowly heated to 90. in the course of 2 hours a viscous brown product is obtained without an exothermic reaction occurring.

The same result is achieved by employing instead of 0.2 c.c. aqueous hydrochloric acid ION 0.1 c.c. diethylsulfate 0.1 c.c. sulfuric acid 10N.

ln ail cases water-soluble, viscous products are obtained that yield on cellulosic materials without the addition of reducing agents yellow dyeings having good fastness properties.

EXAMPLE 4 100 g. Hydrosol Fast Yellow G (see Example la) are suspended in 80 c.c. water. After the addition of 48 c.c. ethylenimine, the reaction mixture is heated to 80 and while maintaining this temperature, S gas is introduced. In the course of this process the temperature of the reaction mixture rises during 12 minutes to 103. After stopping the introduction of SO, gas, stirring is continued for another hour at a bath temperature of 100.

The reaction product, a brown, viscous paste, is easily soluble in water; its behavior in the dyeing is similar to that of the products obtained according to the preceding Examples.

EXAMPLE 5 20 g. lmmedial Fast Yellow GWL (Color lnd. Sulfur Yellow 5; sulfur dyestuff the constitution of which is described in Coll. Czech. Chem. Comm. 2'), (1962) 1533-48) are suspended in 60 c.c. water. After the addition of 24 c.c. ethylenimine, the reaction mixture is heated for 6 hours under reflux. Then it is cooled down to 40 and a further 15 c.c. ethylenimine are added. Subsequently, SO, gas is introduced into the reaction mixture, whereby the temperature reaches 94 in the course of 14 minutes. After the decay of the exothermic reaction, the introduction of the 80, gas is stopped and stirring is continued for another 4 hours at a bath temperature of 100.

Thus obtained is a brown, viscous product that easily dissolves in water.

EXA M PLE 6 100 g. Hydrosol Fast Yellow G (see Example la) are suspended in c.c. water. After the addition of 48 c.c. ethylenimine and 0.1 c.c. epichlorhydrin, SO gas is introduced at room temperature. in the course of the reaction the temperature of the reaction mixture rises within 10 minutes to 102. After the decay of the exothermic reaction, the introduction of SO gas is stopped and stirring is continued for another 4 hours at a bath temperature of The reaction product, a brown viscous paste, is easily soluble in water.

EXAMPLE 7 A mixture of 10 g. lmmedial Fast Yellow GWL (see Example 5) and 50 c.c. ethylenimine is heated under reflux for 3 hours. The brown residue remaining after distilling off the unreacted ethylenimine (38 c.c.) gives a limpid solution, when dissolved in water, which was acidified with acetic acid.

EXAMPLE 8 50 g. lmmedial Fast Yellow GWL (see Example 5) are suspended in 100 c.c. water and boiled with the.addition of 17 g. Na s (60 percent flakes) until the dyestuff is dissolved. The solution is cooled down to 50, 50 c.c. ethylenimine and 0.1 c.c. epichlorhydrin are added and a C0 gas stream is passed through the reaction mixture. In the course of 10 minutes the temperature rises to 100'. After the decay of the exothermic reaction, stirring is continued for another hour at a bath temperature of A brown, viscous product is obtained that gives a limpid solution when dissolved in diluted acetic acid.

EXAMPLE 9 50 g. lmmedial Fast Yellow GWL (see Example 5) are suspended in 75 c.c. water. 17 g. Na s (60 percent flakes) are introduced into the aqueous suspension and heated under reflux until the dyestuff has dissolved. After cooling down to 50, 50 c.c., l,2-propylenimine and 0.1 c.c. epichlorhydrin are added and CO gas is introduced into the reaction mixture. In the course of 10 minutes the temperature rises to 91. After the decay of the exothermic reaction stirring is continued for another hour at a bath temperature of 120. A brown, slightly viscous product is obtained that gives a limpid solution, when dissolved in water, which was acidified with acetic acid.

Analogously the reaction according to the present invention can be carried out with N-acetyl-ethylenimine fl-ethyleniminopropionamide N-methylethylenimine 2,2-dimethylethylenimine 2,3-dimethylethylenimine methyl B-ethyleniminopropionate and 2-ethylethylenimine.

EXAMPLE 1O 50 g. lmmedial Fast Yellow GWL (see Example 5) are suspended in 75 c.c. water. After the introduction of 17 g. Na,S (60 percent flakes), the suspension is heated under reflux until the dyestuff has dissolved. After cooling down to 50, 35 g. B- ethyleniminopropionamide, c.c. ethylenimine and 0,1 c.c. epichlorhydrin are added. Subsequently, CO gas is introduced, whereby the temperature of the reaction mixture rises in the course of 16 minutes to 84". After the decay of the exothermic reaction, stirring is continued for another hour at a bath temperature of 120. Thus obtained is a brown, viscous reaction product that gives a limpid solution when dissolved in diluted acetic acid.

A similar result is obtained if the reaction is carried out with a mixture of 20 c.c. ethylenimine and 30 c.c. propylenimine.

EXAMPLE 1 l a. 100 g. of a green sulfur dyestuff prepared according to the description given in Example 1 of US. Pat. No. 2,395,117, are suspended in 1150 c.c. water. After the addition of 70 g. Na s (60 percent flakes), the suspension is heated under reflux until a deep green solution is formed. After cooling down to 60, 125 c.c. ethylenimine and 10 c.c. epichlorhydrin are added. Subsequently, C0 gas is introduced into the reaction mixture, whereby the temperature rises in the course of 40 minutes to 84". After the decay of the exothermic reaction, the viscous product is stirred for another 30 minutes at a bath temperature of 1 10.

Thus obtained is a viscous, deep green product that gives a limpid solution when dissolved in diluted acetic acid.

b. A cotton cheese bobbin is dyed on the dyeing machine with 5 percent of the thusly obtained dyestuff (liquor ratio 1:10). For this purpose, the dyestuff is dissolved in hot water (60) and diluted by the addition of cold water to adjust the liquor ratio of 1:10, whereby the temperature of the liquor reaches 25-30. Subsequently, the dye liquor is adjusted to a pH value of 7 by the addition of acetic acid, then 5 g./l. urea are added and the dyeing is started with an alternating liquor circulation. After approximately minutes, the dye liquor is heated within 30 minutes to 90-95 and this temperature is kept for 1 hour. Subsequently, the dyed material is rinsed with cold water. In this dyeing process the dyebath is exhausted until it becomes colorless. Thus obtained is a deep green dyeing having an excellent evenness and a good fastness to wet processing.

c. A polyacrylonitrile cotton mixed fabric (50/50) is dyed in a single bath with 3 percent of the green dyestuff obtained according to the above Example 1 1a) and 3 percent Astrazon Orange R (Color Index 48040 Basic Orange 27). The dyestuffs that are separately dissolved in hot water of appr. -80 are brought together and added to the dyebath that was previously admixed with 5 g./l. urea and the pH of which was adjusted to 6 with acetic acid. Dyeing is started at 30, then the temperature is raised within one-half hour to 105 and the dyeing is continued for 1 hour at this temperature. After slow cooling down to 50, the dyed material is thoroughly rinsed, subsequently soaped at -90 and finished after a further rinsing operation. Thus obtained is a bicolor dyeing having very good fastness properties.

d. A paper pulp suspension consisting of 60 kg cellulose fiber 60 kg pulp of bleached pine sulphite 60 kg pulp of bleached sulphate 30 kg cotton linters having a degree of grinding of approx. 40 SR and a solid content of 7 percent by weight is admixed in a hollander beater with the usual additives such as wetting agents, sizing agents and fillers and with 6 percent of a dyestuff solution consisting of 1 part by weight of the dyestuff described in para a) and 3 parts by weight of water. The dyestuff goes immediately onto the fiber and in the subsequent sheet formation on the paper machine, a colorless waste waterv is obtained. The thusly prepared green paper distinguishes itself by excellent fastness properties, in particular by a very good fastness to light and to bleeding out.

EXAMPLE 12 a. 50 g. lmmedial Fast Brown GGL (Color Index 53327) are suspended in c.c. water. After the addition of 50 g. Na s (60 percent flakes), the suspension is heated under reflux until a brown solution is formed. The reaction mixture is then cooled down to 60 and 100 c.c. ethylenimine and 1.0 c.c. epichlorhydrin are added. Subsequently, CO gas is introduced whereby the reaction that takes place immediately is strongly exothermic. The reaction is controlled by cooling so that it ensues under weak reflux. In the course of 50 minutes the temperature of the reaction mixture rises to 102. After the decay of the exothermic reaction, stirring is continued for another 2 hours at a bath temperature of Thus obtained is a brown, viscous product that gives a limpid solution when dissolved in water.

b. 60 g. of the thusly obtained dyestuff are dissolved in 300 c.c. distilled water and filled up with cold water to reach an amount of 1 liter. The liquor being formed has a temperature of 20-25 and the pH value is adjusted with acetic acid to 5. With this liquor a cotton fabric is padded on the padding machine and squeezed off so as to retain 75 percent of its weight of the dye liquor. The impregnated fabric is driedand heated for 1 minute to 200. Obtained is a brown dyeing having very good fastnesses to wet processing.

An improvement of the fixation of the dyestuff is achieved if 10-20 g./l. urea are added to the above padding liquor having a temperature of 25-30 and a pH of 5-7.

The following sulfur dyestuffs were reacted according to the method described in Example 12.

Ex. Sulfur dyestuff Color 11,0 ethy- Na,S Epi- No. Ind. c.c. leng. 60% chlorimine hydrin c.c. c.c.

13 lmmedial lndone 53440 I20 50 30 0.2

RR 50 g. l4 lmmedial Red 53720 100 50 30 0.2

Brown 313 50 g. 15 lmmedial Yellow 53055 100 50 20 0.2

Brown 50 g. 16 lmmedial Orange $3015 100 50 30 0.2

Brown RR 50 g. 17 lmmedial Yellow 53065 100 50 20 0.2

Olive G 50 g. 18 lmmedial Fast 53320 250 50 25 0.2

cutch 4RL 50 g. 19 lndocarbon CL 53290 I00 60 25 0.1

conc. 50 g. 20 lmmedial New 53470 100 50 0.2

Blue FBL 50 g. 21 lmmedial Direct 53235 150 65 0.2

Blue RL 50 g. 22 l-lydron Blue (1 53640 100 100 0.3

50 g. 23 lmmedial Black 53000 100 50 25 0.2

Brown AN 50 g. 24 lmmedial carbon 53185 100 100 30 0.2

CBO 50 g.

The reaction products are viscous dye pastes which are easily soluble in water or diluted acetic acid and yield, when applied without the concurrent use of reducing agents onto cellulosic materials dyeings with good fastness properties.

EXAMPLE 25 50 g. lmmedialcarbon CBO (Color lndex 53185) are suspended, in 80 c.c. water and, after the addition of I00 c.c. ethylenimine, heated during 3 hours under reflux. After cooling down to 60, 0.1 c.c. ethylenechloride are added and subsequently C0, gas is introduced into the reaction mixture, whereby the temperature rises in the course of 12 minutes to 85. After the decay of the exothermic reaction, stirring is continued for another hour at a bath temperature of 120. The reaction product, a viscous, black paste, is easily soluble in water; it yields, when applied onto cellulosic textiles, black dyeings having a good fastness to wet processing.

EXAMPLE 26 50 g. lmmedialcarbon CBO are suspended in 80 c.c. water and heated, after the addition of 100 c.c.

ethylenimine, during 2 hours under reflux. After cool- EXAMPLE 27 50g. lmmedial lndone RR extra (Color Index 53440) are suspended in 80 c.c. water and 48 c.c. ethylenimine are slowly added whereby an exothermic reaction occurs. The introduction velocity of the ethylenimine is controlled so that the reaction takes place under a weak reflux. Towards the end of the reaction the temperature reaches 98. After the decay of the exothermic reaction, stirring is continued for another hour at a bath temperature of 120, the reaction mixture is cooled down to 60 and after the addition of 1.0 c.c. epichlorhydrin, C0 gas is introduced during 15 minutes. Finally, the mixture is heated again for 1 hour at a bath temperature of 120.

The reaction product thus obtained in the form of a viscous blue paste dissolves in an acid aqueous solution having a pH value 6,8.

EXAMPLE 28 50 g. lmmedial Red Brown 38 (Color lndex 53720) are suspended in c.c. water. After the addition of 48 c.c. ethylenimine, the suspension is heated during 3 hours under reflux, and then cooled down to 60. 1.0 c.c. epichlorhydrin are added and CO gas is introduced. In the course of this reaction the temperature reaches 102 within 8 minutes. After the decay of the exothermic reaction, stirring is continued for another hour at 120. The reaction product thus obtained is a brown, viscous paste that easily dissolves in water and yields, when applied without the addition of reducing agents onto cellulosic material, reddish brown dyeings having good fastness properties.

The following sulfur dyestuffs were reacted according to the method described in Example 28 with ethylenimine to form water-soluble products.

Ex. Sulfur dyestutf Color H,O Ethy- Epi- No. Ind. c.c. lenchlorimine hydrin c.c. c.c.

29 lmmedial Yellow Olive 53065 80 48 1.0 56 extra 50 g. 30 lmmedial Green BB 5357] 80 100 1.0 conc. 50 g. 31 lrnmedial Fast Cutch 53320 80 I00 L0 4 RL 50 g. 32 lmmedial Yellow Olive 5G 50 g. 53065 80 100 1.0 33 lrnmedial New Blue 53470 80 100 1.0 FBL 50 g. 34 lmmedial Fast Brown 53327 80 l 00 l .0 GGL 50 g. 35 lndocarbon CL 53290 80 100 L0 50 36 lmmedialcarbon g C80 50 g. 53185 100 48 1.0 37 lmmedial Orange Brown RR 50g. 53015 80 100 1.0 38 lmmedial Orange Brown RR 50 g. 53015 80 48 1.0 39 lmrnedial Yeilow Brown G 50 g. 53055 80 48 1.0 40 Hydrosol Black B l00g. 53l86 I40 l0 0.1 41 Hydrosol Black B 50g. 53186 80 48 L0 EXAMPLE 42 50 g. lmmedial New Blue FBL extra (Color Index 53470) are suspended in 80 c.c. water. Subsequently, 100 c.c. ethylenimine are added dropwise with cooling so that the temperature of the reaction mixture does not exceed After the decay of the exothermic reaction, stirring is continued for 45 minutes at a bath temperature of and subsequently the unreacted ethylenimine, if any, is distilled off in the vacuum. The dyestuff solution thus obtained may be indefinitely diluted with water.

Analogously, the following sulfur dyestuffs were reacted to form water-soluble dyestuffs:

Immedial Fast Brown GGL-Color Index 53327 lndocarbon CL conc.Color Index 53290 Immedialcarbon CBOColor Index 53185 lmmedial lndone RR-Color Index 53440.

EXAMPLE 43 50 g. Hydron Blue G. (Color Index 53640) are suspended in 200 c.c. ethanol and, after the addition of 75 c.c. ethylenimine, heated during 3 hours under reflux. After cooling down, the reaction mixture is sucked off. On the filter there remain 53 g. of a finely pulverizable blue dyestuff that gives a limpid solution if dissolved in acidified water having a pH value of 6.

The deep blue filtrate additionally yields after evaporation to dryness in the vacuum 32 g. of a blue, viscous paste that gives a limpid solution when dissolved in water.

Both reaction products yield, when applied without the addition of a reducing agent, onto cellulose fibers deep blue dyeings having good fastness properties.

EXAMPLE 44 50 g. lmmedial lndone RR extra (Color Index 53440) are suspended in 200 c.c. methanol and, after the addition of 75 c.c. ethylenimine, heated during 3 hours under reflux. After cooling down, the reaction mixture is filtered, whereby 52 g. of a blackish brown dyestuff powder are isolated that dissolves in acidified water having a pH value 6 with a blue color.

By evaporating the filtrate in the vacuum, 72 g. of a pasty residue are obtained that dissolves in water with a blue color.

The solid and the pasty reaction product yield, when applied onto cellulosic materials, blue dyeings having good fastness properties.

EXAMPLE 45 g. of a green sulfur dyestuff prepared according to the description given in Example 1 of US. fat. No. 2,395,117 are suspended in 230 c.c. dimethylformamide and heated to After the addition of 14 g. Na S (60 percent flakes), a deep blue dyestuff solution is formed. The temperature is then raised to where it is kept for 30 minutes. 0.2 c.c. epichlorhydrin and 25 c.c. ethylenimine are then added to the solution which has cooled down to 60. Subsequently, CO gas is introduced into the reaction mixture, whereby the temperature reaches 80 within 15 minutes.

After the decay of the exothermic reaction, stirring is continued for another hour at a bath temperature of The reaction product, a slightly viscous, green solution can be indefinitely diluted with acidified water having a pH value 6.

When applied without the addition of reducing agents onto cellulose fibers, this solution yields clear green dyeings having good fastness properties.

Analogous results are obtained by performing the reaction in mixtures consisting of water and dimethylformamide.

What is claimed is: l. A water-soluble sulfur dyestuff capable of dyeing textile materials in the absence of a reducing agent, said dyestuff being the product of reaction of a waterinsoluble sulfur dyestuff, a reduction product thereof or a thiosulfuric acid derivative thereof at a temperature of from 15 to C. with a member selected from the group consisting of ethylenimine, 1,2- propylenimine, N-acetylethylenimine, B- ethyleniminopropionamide, N-methylethylenimine, 2,2-dimethylethylenimine, 2,3-dimethylethylenimine, methyl-B-ethyleniminepropionate and 2- ethylethylenimine until a water-soluble dyestuff is obtained.

2. The water-soluble sulfur dyestuff of claim 1 wherein said reaction is carried out at a temperature of from 40 to 120 c.

3. The water-soluble sulfur dyestuff of claim 1 wherein, during said reaction, the pH is lowered to about 4 to 5.

4. The water-soluble sulfur dyestuff of claim 1 wherein said reaction is carried out in the presence of CO or $0 5. The water-soluble sulfur dyestuff of claim 1 wherein said reaction producing the same is carried out in the presence of a catalytic amount of ethylenechloride or epichlorhydrin. 

1. A water-soluble sulfur dyestuff capable of dyeing textile materials in the absence of a reducing agent, said dyestuff being the product of reaction of a water-insoluble sulfur dyestuff, a reduction product thereof or a thiosulfuric acid derivative thereof at a temperature of from 15* to 120* C. with a member selected from the group consisting of ethylenimine, 1,2-propylenimine, N-acetylethylenimine, Beta -ethyleniminopropionamide, N-methylethylenimine, 2,2-dimethylethylenimine, 2,3-dimethylethylenimine, methyl- Beta -ethyleniminepropionate and 2-ethylethylenimine until a water-soluble dyestuff is obtained.
 2. The water-soluble sulfur dyestuff of claim 1 wherein said reaction is carried out at a temperature of from 40* to 120* C.
 3. The water-soluble sulfur dyestuff of claim 1 wherein, during said reaction, the pH is lowered to about 4 to
 5. 4. The water-soluble sulfur dyestuff of claim 1 wherein said reaction is carried out in the presence of CO2 or SO2. 